Decachlorotetrahydro-4,7-methanoindeneone pesticide and method for combating noxiousorganisms therewith



DECACHLOROTETRAHYDRO -4-, 7- METHANO/NDENEONE 9-0 /0.0 WAVE LENGTH IN MICRONS A X O.l"/ WATER 5 0.84% WATER C= 2.86% WATER D= CARBON D/SULPH/DE SOLVENT INVENTORS. EVERETT E. GILBERT SILVIO L. GIOLITO BY z ATTORNEY.

Patented Nov. 4, 1952 INDENEONE PESTICIDE AND METHOD FOR COMBATING NOXIQUS ORGANISMS' THEREWITH Everett E. Gilbert, Flushing. and Silvio L. Giolito, 7

New

York, N. Y., assignors to Allied Chemical & Dye Corporation, New York, N. Y., a corporation of New York Application November 17, 1950, Serial No. 196,121 (or. nap-30) 11 Claims.

This invention relates to a new pesticidal composition comprising decachlorotetrahydro-4,7- methanoindeneone and to a method for combating noxious organisms therewith.

The decachlorotetrahydro-4,7-methanoindeneone compositions of our invention are useful in combating a wide variety of noxious organisms including insects and their larvae of the Hymenoptera (flies), Lepidoptera (moths), Coleoptera (beetles) and Orthoptera (grasshoppers) species, and also in combating crop-attacking fungi.

The compositions of our' invention comprise essentially a decachlorotetrahydro-4,7-methanoindeneone, usually in hydrate form, which may be applied alone orin association with a spray or dust carrier material in any suitable manner adapted to combat the particular organism to be controlled. As a spray or impregnant, the :solid decachlorotetrahydro-4,7-methanoindeneone may conveniently be dissolved or dispersed .in any standard liquid carrier, such as kerosene or the like. As a dust, it may be mixed with a :suitable finely divided solid material, such as clay or the like. It may readily be applied from solu- :alcohols with water or kerosene. Application of decachlorotetrahydro-4,'7-methanoindeneone in liquid solution form is moth-proofing of fabrics and to control of house- :flies and the like, while application in the form one is a white crystalline solid with no appre- Upon heating in a glass melting ample, slight sublimation occurs upon oven drying at 1l0-115 C., while upon heating at 140 C. at 1-1.5 mm. of Hg pressure, 10-15% of its weight sublimes in three hours. It sublimes with some decomposition when heated in the open atmosphere to 300 C. It is readily soluble and is useful for insecticidal, etc., purposes in The decachlorotetrahydro-4;7-methan0indene- 'of dusts or liquid sprays may conveniently be used in its application to vegetable crops and the like, to control infestations of insects orjungi, whereas grain or flour infesting organisms may 'be controlled by the addition of small quantities of undiluted decachlorotetrahydro-4,7methanofindeneone directly tothe grain material.

The decachlorotetrahydro4,7-methanoindeneone hydrate is characterized by the following chemical analysis:

The decachlorotetrahydro-4,7-methanoindeneamoth-proofing agent.

In the accompanying figure, the several lines represent the infared spectrogram of the decachlorotetrahydro-i,7-methanoindeneone, which is the essential toxic ingredient of the new pesticidal composition of our invention. The spectrorams were obtained in carbon disulfide solutions of samples of difierent degrees hydration; dotted line Abeing the record of substantially anhydrous pound serves as an accurate means for identifymaterial (0.10% or 0.03 mol H2O); solid line B ing the compound. It has been compared with being the record of a slightly hydrated sample a human fingerprint in its ability to identify a (0.84% or 0.24 mol H2O); while solid line C is compound with certainty. The characteristic the record of an essentially monohydrated sam- 5 reproducibility of the infrared spectrogram of a ple (2.86% or 0.8 mol H2O). The three spectrogiven compound is due to the facts that when grams are considered. substantially identical. a-molecule is excited by infrared radiation it Solid line D is the spectrogram of the CS2 solvent. absorbs energy to a greater degree at some wave These infrared spectrograms were prepared on length than at others, and that the amount of a standard infrared recording spectrophotometer absorption depends on the configuration and designed for measuring and recording the infraupon the linkages of the atoms composing the red transmission of solids, liquids and gases, commolecule. Accordingly, the compound is identiprising a double infrared beam which scans the ;fied and characterized with certainty by its inspectrum through the wave length range 2.0 to frared spectrogram.

16 microns, one part of the beam passing through The new pesticidal composition of our inventhe sample under study, .the other passing tion may be prepared by any suitable process, through a compensating cell. ,If the sample for example by condensing two molecules of under study absorbs radiation, the two beams hexachlorocyclopentadiene with the aid of sulfur become unequal. The magnitude of this inequaltrioxide to form a hexachlorocyclopentadiene reity is a measure of the transmission of the sample 20 action product and hydrolyzing the reaction of the particular wave length, and the record of Y productto the ketone as described in copending these differences within the range of wave lengths application Serial No.-:196,123 filed November 1'7,

scanned is the infrared srnec t rogram reeorded as 1950; or by reacting hexachlorocyclopentadiene an ink drawn line one. chart graduated in perwitha halosulfonic'acid, such as chlorosulfonic cent transmission as ordinates andin wave length acid and fluosulfonic acid. and hydrolyzi-ng the as abscissae. v I I resulting reaction product to 'form the ketone,

Solid samples, such as the compound of our Theexact mechanism of the reactions involved invention and the related compounds vdescribed, in the preparationo'f the'-decachlorotetrahydroare conveniently measured insolution. The spec- 4,7-methanoindeneone product is not clearly trograms shown in the figures were'all measured understood, but the overall reaction is indicated by dissolving 0.5 gram of the solid in carbon diin the equation set forth below:

c1-c-o-o1 01-0 0-0-o1 S0101 Halo sou: Cl

2 followed by C hydrolysis \C1 o1-o o'-c1 01- /c /c-c1 c\ o L e 0K 01 a t Hexachlorocyclopentadiene 2,3,3a,4,5,6,7,7a,8,S-decachloro-Ba,

4,7,7a-tetrahydro4,7-methanoindene-l one sulfide and diluting to 10 ml. with the solvent. While the overall reaction in the methods of A small amount of the solution was then intropreparation described above proceeds from the duced into a, liquid cell with sodium chloride same starting material to the same end product windows and sealed. The cell was placed in the when carried out using the S03 treatment and spectrophotometer in the path of one of the when using the halosulfonic acid treatment, the

beams as described above. e r reaction mechanisms'prob'ably' differ and are be- The infrared spectrogramof any chemical comlieved to proceed somewhat as illustrated below:

oi-c --c-c1 Cl-C /Cl 2 280 I Cl Ci-G C--Ci 01-0 c ci t1 rosoici smoi Cl Cl d Cl /o1 01 -0- c --c-'-c1 oi-c o--o-c1 5 Y +2n,so.+2rro1 Cl c1 01- Q c-o1 o1-c 0 0-01 trality, or to a very decachlorotetrahydro methanoindeneone and sulfur trioxide. ,i

The liquid S03-hexachlorocyclopentadiene reaction product thus formed is then hydrolyzed to the decachloromethanoindeneone, by drownhydrolysis.

The product desired, but to reprecipitates. The amount eutralization should be sufiimixture preferably to neuslight alkalinity not exceed- NaOH, as indicated by a pH of crystalline product of acid added for n cient to bring the ing' about 0.05% 7-8.

After neutralization, the charge is. agitated, preferably at a temperature between about 90 C. and about 95 (1., for about a half hour While maintaining the mixture at the neutral point or slightly on the alkaline side.

The mixture is then cooled, for example to room temperature to insure relatiyely complete precipitation of the product, leavingin solution half hour, during 3 c 01., c1 o1 -o c-c1 CIC I EOLGCI 2 1:30.: 5, 13 I BK V l Cl L c1-o co1 01-0 0-01 *1. 01 Cl $1 b osmx 1+ 3H10 21 01 c 01 o1 O]C/ C C-Cl 01-02 I 0*0-01 c1 c1 -Hn0 C\ s C\ ZHX 1.3.3801 '010 I 01 c c 01 010 c 01 l a /l\ 1 01 1 l 11 (11 'H O I I wherein X=chlorine or fluorine .25 the salts formed in the neutr In carrying out the process vfor preparing the alkali metal or ammo Dried Dried ried 'In carrying out thedecac halosulfonic acid.

(The solid nic acid reaction produc the hexachlorocyclo fonic acid reaction product 1 we or fl s mm ac Theory for anh eory for mo ,Theory for di hexachlorocyclopentadiene Comment ydrous compound. nohydrate. hydrate.

18 hours at 90 C 72 hours at 90 C.

72 hours at 27 C.

-halosulpentadiene-halosul may be chlorosulused either alone,

or dissolved in a solvent which is inert to the reaction such as tetrachloroethylene.

action may be somewhat higher than that used when S: is the condensing agent and maybe carried as high as 140 C., if desired, and thus effeet a reduction in the time necessary for com-- pletion of the reaction over that necessary when peratures between about 90 C. and about 120 C.- are satisfactory to effect completion of the condensation reaction in from about to about 2 hours, respectively.

The molar ratio of halosulfonic acid to hexachlorocyclopentadiene product should be at least about 1: found that ratios between about 1.25:2 and about 8:2 are satisfactory.

The hydrolysis of the hxachloro'cyclopentadienehalosulfonic acid reaction products to decaqueous caustic alkali solution, a water solution. hydrolysis, probably because of the'lo'w solubilit'ies of these reaction products in water. iiri'the case of the chlorosulfonic acid product, hydroysi's may be carried out in aqueous lower aliphatic alcohol solution which appears to impart sufficient solubility to the reaction product to promote hydrolysis. However, the fiuosulfonic acid reaction product requires at least some alkali in the solution for adequate hydrolysis. Temperatures at which the hydrolyses are carried out are not particularly critical, but preferably should be at least about 30 C., and temperatures between about 60 C. and about 90 C., that is, temperatures. in the vicinity of the boiling points of thelower aliphatic alcohols are satisfactory.

In general, no digestion step is necessary following the hydrolysis of the hexachlorocyclopentadienehaiosulfonic acid reaction products as the decachlorotetrahydromethanoindeneone product precipitates readily from the reaction mixture upon acidification with aqueous mineral acids.

The toxicity characteristics of our new decachlorotetrahydro-4,7-methanoindeneone (designated DTMC) in the tables) against various pest organisms are indicated by the following tests, results of which are tabulated below.

Comparative tests were run with DDT and the new compound of our invention (DTMO) on laboratory reared DDT-resistant housefiies, with results as shown in Table II. Tests were run by spraying the flies with a solution of toxicant in spray oil (U1trasene brand deodoriz'ed kerosene).

Toxicity of DTMO to nouseflie s s D n Alive Dead I PercenttDead Treatment F ee-. e-

Males males Males males 'inales 5 59 56 l 0 are "0'.

-DTMO $135075. Q 52 53- 100.0. 73. DDT {it 0.25%. 27 69 18 3 40.0 4. DDT at 0.50% 8 39 53 3 86.9 7. .Check 29 .0 I 0 0- 0 0.

Our new compound was compared-with 2,33 5,- '63,8,8-octachlorotetrahydro-4,7 -'methanoindane The temperature of the initial condensation re for good yields of reaction,

2, and we have I Toxicity of DTMO to hoiisflies lower temperatures are employed. Usually teme r Isopropanol,25

, Check (no toxlcant) 2o achlorotetrahydromethanoindeneone may-be ef fected by heating the reaction product with an;

(Chlordane) against flies in tests in which panels were sprayed with solutions of the toxicant's with results shown in Table III.

TABLE 111 vs. Chlordane I No. knocked down after 8 hrs. hm

hrs.

DTMO, 5% Isopropanol, Ultrasene, 70% Chlordane, 5%

Ultrasene, 70%

The tests recorded in-Table IVcompare DTMO "with DDT (both as 5% dusts) against southern armyworms and Mexican bean beetle larvae.

alone being ineffective to accomplish complete m 12mm; may, 91%

(Toxicity of DTMO to cockroaches TABLE 1v 1 .Torti city or DTMO to armyworms m bean beetles vsLDDT Percent Kill Against- ,Treatment Armyworms B. B. Larvae DTMO, 3%; Cl y, 97%.

Results on American cockroaches are shown in Table-V below, using two hundred mg. of dust for each test.

' TABLE v I No. knocked down after- Results on stored grain insects, i. e. bean weevil and confused flour beetle are shown in Table VI.

TABLE VI Toxicity of DTMO tograin, insects Percent Kill:

Check (no toxicant) carpet beetle larvae are customarily used in i5 evaluating moth-proofing characteristics of woolsince they are larvae 01"" thesame general type asthose of the clothes moth and they not only are in general significantly more resistantto toxicants :thantheclothes moth larvae, but are actuas moth damage. I carpet beetle larvaeas test organisms were carried out by soaking woolen swatches in 1%. acetone solution of our. decachlorotetrahydromethanoindeneone and {DD'I'f for comparison. The

' TABLE VI: Toxicity of DTMO to carpet beetles vs. DDT

Observations At 1' Three ee Percent No.v 52 5;851:1 2

Deposit Dry on Cleangfi; Swatch ings V Treatment 2. 8 2' 2.1 20. Trace.

2. 2 1 2. 2 20 None.

2. 4 1 2. 3 19 Trace 2. 8 20 None 2. 7 2 1. 7 7 Trace.

2. 5 1 1.6 5 Do. 3. 0 1 1. 8 14 D0. 2. 3 0 20 None.

It is evident from the results shown in Table VII that not only is our compound more destructive to the carpet beetle larvae than is DDT, but that it is more resistant than DDT to dry cleaning, being an eiTective toxicant even after at least two cleanings.

The prolonged insecticidal efiectiveness of our compound is indicated by the results recorded in Table VIII. In the reported tests, bean plants were dusted with 3% dusts of our compound and of Chlordane respectively, then infested with 6th instar southern armyworms at the time intervals indicated.

TABLEVIII Residual insecticidal activity of DTMO vs. Chlordane Age of Deposit Fungicidal properties of our compound against early blight of potatoes (Alternaria solam') are spray applications in the standard manner at about two week intervals in comparison with the results obtained with the test insecticide alone.

TABLE I Toxicity of DTMO tozvard fungi Percent' as After g Treatment DTMO -i-Test Insecticide 1 16.25 406 Test Insecticide Alone 3 31. 0 358 R 1 25% DTMO+75% clay-5 lb./l00 gels. of water.

2 Test insecticide(25% dichlorodiphenyltrichloroethane+3% para nitro phenyl diethyl thiono phosphate in a petroleum emulsion) at the rate of 1 lb. of emulsion per 800 gals. of water.

3 1 lb./400 gals.

TA E X Toxicity of DTMo to grasshoppers vs. Chlordane Pounds Percent Kill Insecticide Applied 24 hrs. I 72 hrs. DTMO V Y 1 to Chlordane" s 1' 75 Our compound, n'iike'd' with the same test in secticide described in Table IX, was applied to treatment with our compound over that when the test insecticide alone was used.

TABLE XI Toxicity of DTMO to several potato infesting insects No. of Organisms Caught by Sweeping After Fourth reatment Bu. per Insecticide N Am Flea Plant Leaf Beetle Bugs Hoppers DTMO CompJ+Test Insecticide 1 5 3 2 304 Test Insecticide 61 15 3 220 1 25% DTMO+75% clay-6 lbs/800 gels. of Water. 7

I 25 DDT and 3% p-nltrophenyl dlethyl thiono phosphate in a petroleum emulsion-1 lb. of emulsion per 800 gels. of water.

3 As 1lb./400 gels. of water.

While the above describes the preferred embodiments of our invention, it will be understood the scope of the specification and claims.

We claim:

essential active ingredient a. decachlorotetrahydro-4,7-methanoindeneone and a pesticidal adjuvant therefor.

2. A pesticidal composition as defined in claim 1 wherein said active ingredient is dissolved in a a pesticidai adjuvant. comprising a liquid organic solvent for'the actiye ingredient. 3. A fie'sticidal composition as aefinea'm claim 1 wherein said active ingredient is dissolved in a pesticidal adjuvant comprising a hydrocarbon liquid solventffor the active ingredient.

45A pesticidal composition comprising as its essential. active, ingredient a decachlorotetra: hydro-4,7-rnethanoindeneone admixed with a water-insoluble solid diluent as pesticidal adjuvant therefor, both in finely divided form.

5. A pesticidal dusting powder mprising a minor proportion of. a finely divided decachlorotetrahydro-4,'Z=methanoindeneone as its essential active ingredient admixed with a major proportion of: fixfiei-y divided olay as pesticidal adjuvanptn rerorg; 6: A-metfiod for eombatingnoxious pest organ isms which comprises contacting; said organisms active ingredient a decachlorotetiahydro4;?- methanoindeneone.

met p f wi be i s n ec of the h menoptra species-men com sescontacting said insects with a composition containing as an essential active ingredient a decachlorotetrahydro=4-,'7'=methanoindeneone.

8. A method for combating insects of the lepidoptera species which comprises contacting said insects with; a composition containing as an essential active ingredient a decachlorotetrardrqr flrmsthamnide egerms witheir composition containing as an essential '9'? A method 61" comnating insects urine ieo tera species which comprise contacting said insects with a composition containing as an e'ssentiai active ingredienta decachiorotetrahydro-4,l methanoindeneone. H

10. A method for combating insects of the orthopter'a species which comprises contacting said insects with a composition containing as anesse ntialactive ingredient a decachlorotetrahydro-4,7-methanoinde n 11. A methedfor combating fungi which confiprises contacting saidfungi with a composition containing as an essential active ingredient a decachlorotetrahydro-fl methanoindeneone.

EVERETT E; GILBERT; SILVIO L. GIOLITO.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS OTHER REFERENCES Newcomer et aL: J. Am. Chem. Soc., volume '71-, pages 946; 9 51, Mareh 1949);. 

1. A PESTICIDAL COMPOSITION COMPRISING AS ITS ESSENTIAL ACTIVE INGREDIENT A DECACHLOROTETRAHYDRO-4,7-METHANOINDENEONE AND A PESTICIDAL ADJUVANT THEREFOR. 